P
US7500397B2ActiveUtilityPatentIndex 92

Activated chemical process for enhancing material properties of dielectric films

Assignee: AIR PROD & CHEMPriority: Feb 15, 2007Filed: Jan 31, 2008Granted: Mar 10, 2009
Est. expiryFeb 15, 2027(~0.6 yrs left)· nominal 20-yr term from priority
Inventors:WEIGEL SCOTT JEFFREYO'NEILL MARK LEONARDVRTIS RAYMOND NICHOLASSINATORE DINO
H10P 14/6922H10P 14/6686H10P 14/6336H10P 14/665H10P 95/00H10P 95/90H10P 14/6342
92
PatentIndex Score
30
Cited by
37
References
46
Claims

Abstract

A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of: contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid; and exposing the at least one surface of the layer of silicon-containing dielectric material to an energy source selected from the group consisting of: UV radiation, heat, and an electron beam, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source.

Claims

exact text as granted — not AI-modified
1. A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of:
 contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid; and 
 exposing the at least one surface of the layer of silicon-containing dielectric material to an energy source selected from the group consisting of: UV radiation, heat, and an electron beam, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source. 
 
   
   
     2. The method of  claim 1  further comprising the step of removing a first portion of the silicon-containing fluid such that a second portion of the silicon-containing fluid remains in contact with the at least one surface of the layer of silicon-containing dielectric material, wherein the removing step occurs between the contacting step and the exposing step. 
   
   
     3. The method of  claim 1  further comprising the step of exposing the layer of silicon-containing dielectric material to a low-energy plasma source prior to exposing the layer of silicon-containing dielectric material to the energy source. 
   
   
     4. The method of  claim 3  wherein the layer of silicon-containing dielectric material is exposed concurrently to the plasma energy source and at least one energy source selected from the group consisting of: UV radiation, thermal energy, and an electron beam. 
   
   
     5. The method of  claim 3  wherein the layer of silicon-containing dielectric material is exposed to the plasma energy source before it is exposed to the at least one energy source selected from the group consisting of: UV radiation, thermal energy, and an electron beam. 
   
   
     6. The method of  claim 1  wherein the energy source comprises UV radiation. 
   
   
     7. The method of  claim 6  wherein the energy source further includes thermal energy. 
   
   
     8. The method of  claim 6  wherein the UV radiation is monochromatic UV radiation. 
   
   
     9. The method of  claim 1  wherein the contacting step is performed by a chemical vapor deposition process. 
   
   
     10. The method of  claim 9  wherein the silicon-containing fluid is at least one selected from the group consisting of: methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethoxymethylsilane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, bis(dimethoxyphenylsilyl)methane, bis(diethoxyphenylsilyl)methane, bis(methoxydimethylsilyl)methane, bis(ethoxydimethylsilyl)methane, bis(methoxydiphenylsilyl)methane, bis(ethoxydiphenylsilyl)methane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisialzane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, methyltriacetoxysilane, methylethoxysilacyclopropane, hexamethylsilabutane, dimethyldiacetoxysilane, and di-tert-butoxydiacetoxysilane. 
   
   
     11. The method of  claim 10  wherein the silicon-containing fluid is at least one selected from the group consisting of: hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasilane, dodecamethylcyclohexasilane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, dimethydimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane. 
   
   
     12. The method of  claim 11  wherein the silicon-containing fluid is at least one selected from the group consisting of: diethoxymethylsilane, dimethyldiacetoxysilane, methyltriacetoxysilane, di-tert-butoxydiacetoxysilane, dimethyldimethoxysilane, and methyltriethoxysilane. 
   
   
     13. The method of  claim 10  wherein the silicon-containing fluid comprises at least one of octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane. 
   
   
     14. The method of  claim 12  wherein the silicon-containing fluid comprises dimethyldiacetoxysilane, methyltriacetoxysilane, and acetoxytrimethylsilane. 
   
   
     15. The method of  claim 1  wherein the contacting step is performed by a spin-on deposition process. 
   
   
     16. The method of  claim 1  wherein the layer of silicon-containing dielectric material is porous. 
   
   
     17. The method of  claim 1  wherein the first dielectric constant is from about 1.5 to about 3.5, the second dielectric constant is from about 5% to about 200% higher than the first dielectric constant and the third dielectric constant is from about 10% to about 150% restored relative to the second dielectric constant. 
   
   
     18. The method of  claim 17  wherein the first dielectric constant is from about 1.5 to about 2.8. 
   
   
     19. The method of  claim 18  wherein the first dielectric constant is from about 1.8 to about 2.7. 
   
   
     20. The method of  claim 1  wherein the layer of silicon-containing dielectric material has a dielectric constant that is within 10% of the third dielectric constant after exposure to a temperature of at least 400° C. 
   
   
     21. The method of  claim 1  wherein the silicon-containing fluid comprises at least one selected from the group consisting of: a linear silazane, a cyclic silazane, a cyclic organosiloxane, an organosiloxane, an alkylalkoxysilane, an alkylacetoxysilane, an alkylchlorosilane, a carbosilane, an aminoalkylsilane, an alkylaminoalkylsilane, and an aminoalkylalkoxysilane. 
   
   
     22. The method of  claim 21  wherein the silicon-containing fluid comprises an alkylacetoxysilane. 
   
   
     23. A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of:
 contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid; 
 removing a first portion of the silicon-containing fluid such that a second portion of the silicon-containing fluid remains in contact with the at least one surface of the layer of silicon-containing dielectric material; and 
 exposing the at least one surface of the layer of silicon-containing dielectric material to UV radiation and thermal energy, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source. 
 
   
   
     24. The method of  claim 23  further comprising the step of exposing the layer of silicon-containing dielectric material to a low-energy plasma source prior to exposing the layer of silicon-containing dielectric material to the energy source. 
   
   
     25. The method of  claim 23  wherein the UV radiation is monochromatic UV radiation. 
   
   
     26. The method of  claim 23  wherein the contacting step is performed by a chemical vapor deposition process. 
   
   
     27. The method of  claim 26  wherein the silicon-containing fluid is at least one selected from the group consisting of: methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethoxymethylsilane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, bis(dimethoxyphenylsilyl)methane, bis(diethoxyphenylsilyl)methane, bis(methoxydimethylsilyl)methane, bis(ethoxydimethylsilyl)methane, bis(methoxydiphenylsilyl)methane, bis(ethoxydiphenylsilyl)methane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, methyltriacetoxysilane, methylethoxysilacyclopropane, hexamethylsilabutane, dimethyldiacetoxysilane, and di-tert-butoxydiacetoxysilane. 
   
   
     28. The method of  claim 27  wherein the silicon-containing fluid is at least one selected from the group consisting of: hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasilane, dodecamethylcyclohexasilane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, dimethydimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane. 
   
   
     29. The method of  claim 28  wherein the silicon-containing fluid is at least one selected from the group consisting of: diethoxymethylsilane, dimethyldiacetoxysilane, methyltriacetoxysilane, di-tert-butoxydiacetoxysilane, dimethyldimethoxysilane, and methyltriethoxysilane. 
   
   
     30. The method of  claim 29  wherein the silicon-containing fluid comprises at least one of acetoxytrimethylsilane, methyltriacetoxysilane, and dimethyldiacetoxysilane. 
   
   
     31. The method of  claim 23  wherein the layer of silicon-containing dielectric material is porous. 
   
   
     32. The method of  claim 23  wherein the first dielectric constant is from about 1.5 to about 3.5, the second dielectric constant is from about 5% to about 150% higher than the first dielectric constant and the third dielectric constant is from about 10% to about 150% recovered relative to the second dielectric constant. 
   
   
     33. The method of  claim 32  wherein the first dielectric constant is from about 1.5 to about 2.8. 
   
   
     34. The method of  claim 33  wherein the first dielectric constant is from about 1.8 to about 2.7. 
   
   
     35. The method of  claim 23  wherein the layer of silicon-containing dielectric material has a dielectric constant that is within 10% of the third dielectric constant after exposure to a temperature of at least 400° C. 
   
   
     36. The method of  claim 23  wherein the silicon-containing fluid comprises at least one selected from the group consisting of: a linear silazane, a cyclic silazane, a cyclic organosiloxane, an organosiloxane, an alkylalkoxysilane, an alkylacetoxysilane, an alkylchlorosilane, a carbosilane, an aminoalkylsilane, an alkylaminoalkylsilane, and an aminoalkylalkoxysilane. 
   
   
     37. The method of  claim 36  wherein the silicon-containing fluid comprises an alkylacetoxysilane. 
   
   
     38. A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of:
 contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid comprising an alkylalkoxysilane; 
 removing a first portion of the silicon-containing fluid such that a second portion of the silicon-containing fluid remains in contact with the at least one surface of the layer of silicon-containing dielectric material; and 
 exposing the at least one surface of the layer of silicon-containing dielectric material to UV radiation and thermal energy, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source. 
 
   
   
     39. The method of  claim 38  wherein the alkylalkoxysilane is at least one selected from the group consisting of: methyltriethoxysilane, methyltrimethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and trimethylpropoxysilane. 
   
   
     40. The method of  claim 39  wherein the alkylalkoxysilane is methyltriethoxysilane. 
   
   
     41. The method of  claim 39  wherein the alkylalkoxysilane is dimethyldimethoxysilane. 
   
   
     42. The method of  claim 38  wherein the layer of silicon-containing dielectric material is porous. 
   
   
     43. The method of  claim 42  wherein the first dielectric constant is from about 1.5 to about 3.5, the second dielectric constant is from about 5% to about 150% higher than the first dielectric constant and the third dielectric constant is from about 10% to about 150% recovered relative to the second dielectric constant. 
   
   
     44. The method of  claim 43  wherein the first dielectric constant is from about 1.5 to about 2.8. 
   
   
     45. The method of  claim 44  wherein the first dielectric constant is from about 1.8 to about 2.7. 
   
   
     46. The method of  claim 38  wherein the layer of silicon-containing dielectric material has a dielectric constant that is within 10% of the third dielectric constant after exposure to a temperature of at least 400° C.

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